Phenylpyrazole fungicides

ABSTRACT

Phenylpyrazoles of the formula: ##STR1## in which: X=H, hal, NO 2 , CN, SCN, alkyl (C 1  -C 4 ), alkenyl (C 2  -C 4 ), alkynyl (C 2  -C 4 ), alkoxy (C 1  -C 4 ), alkylthio (C 1  -C 4 ), phenyl, phenoxy; mono- or di- alkyl- or phenyl- amino; alkylcarbonyl, carbamoyl, carboxyl, benzoyl; alkyl- sulphinyl or sulphonyl; 
     Y, Z=H, hal, OH, NO 2 , NO, CN, SCN, alkyl (C 1  -C 4 ), alkenyl (C 2  -C 4 ), alkynyl (C 2  -C 4 ), alkoxy (C 1  -C 4 ), alkylthio (C 1  -C 4 ), phenyl, phenoxy; mono- or di- alkyl- or phenyl- amino; alkylcarbonyl, carbamoyl, carboxyl, benzoyl; alkyl- sulphinyl or sulphonyl, for example; and 
     Y, Z may also form a bridge of 1 to 4 atoms, of which at least one can be a hetero atom, optionally substituted. The products are useful as fungicides in agriculture.

This application is a divisional of application Ser. No. 07/959,131,filed Oct. 9, 1992.

The present invention relates to new derivatives of the 3-phenylpyrazolefamily, to processes for their preparation, to the compositions whichcontain them and to their use for the protection of plants againstfungal diseases.

More especially, the subject of the invention is 3-phenylpyrazolederivatives, characterised in that they are of formulae: ##STR2## inwhich: X is:

a hydrogen or halogen atom,

a nitro, cyano or thiocyanato group,

an alkyl, alkenyl alkynyl, alkoxy or alkylthio group, each of thesegroups being halogenated or nonhalogenated,

a phenyl or phenoxy group, each of these groups being optionallysubstituted by C₁ -C₃ alkyl, C₁ -C₃ haloalkyl or C₁ -C₃ alkoxy,

an amino substituted or unsubstituted by one or two alkyls or phenyls,

an alkylcarbonyl, carbamoyl, carboxyl or benzoyl group,

an alkylsulphinyl or alkylsulphonyl group, it being understood that thealkyl part of all the above groups comprises 1 to 4 carbon atoms unlessotherwise defined, and the alkenyl and alkynyl groups contain 2 to 4carbon atoms;

Y and Z, which are identical or different, are:

a hydrogen atom, but not together, or halogen atom, a hydroxyl, nitro,nitroso, cyano or thiocyanato group, or an amino substituted orunsubstituted by one or two alkyls or phenyls,

an alkyl, alkoxy or alkylthio, hydroxyalkyl, alkenyl, alkynyl,alkylsulphinyl or alkylsulphonyl group, the alkyl part of these groupscomprising 1 to 4 carbon atoms and being able to be halogenated;

phenyl, phenyloxy or phenylthio or benzyl, substituted or unsubstitutedon the nucleus by C₁ -C₃ alkyl, C₁ -C₃ haloalkyl or C₁ -C₃ alkoxy,

a formyl, acetyl, alkyl- or alkoxy(thio)carbonyl, mono- ordialkylaminocarbonyl or mono- or dialkylaminothiocarbonyl, carboxyl,carboxylate or carbamoyl group, the alkyl part of these groupscomprising 1 to 4 carbon atoms and being able to be substituted by atleast one halogen atom,

or benzoyl, substituted or unsubstituted on the nucleus by C₁ -C₃ alkyl,C₁ -C₃ haloalkyl or C₁ -C₃ alkoxy;

Y and Z can also be joined together via a carbon bridge comprising 1 to4 atoms, at least one of which can be replaced by an oxygen, sulphur ornitrogen atom, it being possible for the carbons of this bridge toadditionally be substituted or unsubstituted by at least one halogenatom and/or at least one alkyl, alkoxy or alkylthio group as definedabove, and it being possible for each to be also joined, via a doublebond, to an oxygen atom;

R is:

a) hydrogen, nitro, amino, hydroxyl, cyano, alkyl or haloalkyl, eachcomprising 1 to 6 carbon atoms, or a phenyl substituted or unsubstitutedby at least one halogen atom, one nitro group or haloalkyl containing 1to 3 carbon atoms;

b) a group S(O)_(m) --R₁, in which:

m is an integer equal to zero or two, and

R₁ is:

either, when m is equal to zero:

a haloalkyl group containing 1 to 6 carbon atoms,

a phenyl or 3-pyridyl, it being possible for each to be substituted byat least one halogen atom or one nitro, alkyl, haloalkyl, alkoxy orhaloalkoxy group, the alkyl part of these four groups comprising 1 to 4carbon atoms;

or, when m is equal to two:

an alkyl or alkoxy group, each comprising 1 to 6 carbon atoms and beingsubstituted or unsubstituted by one or more halogen atoms or alkoxygroups containing 1 to 3 carbon atoms;

a cycloalkyl group containing 3 to 6 carbon atoms;

an alkenyl or alkynyl or alkenoxy group, each comprising 3 to 6 carbonatoms;

a phenyl group, substituted or unsubstituted by 1 to 5 substituentschosen from the group comprising a halogen atom, a nitro group or analkyl, haloalkyl, alkoxy or haloalkoxy comprising 1 to 4 carbon atoms;

c) a group CH₂ --NR₂ R₃, in which:

R₂ is:

alkyl containing 1 to 6 carbon atoms, optionally substituted by asubstituent chosen from the group comprising cyano, alkoxy, cycloalkylcontaining 3 to 7 carbon atoms, alkylcarbonyl, alkoxycarbonyl, mono- ordialkylaminocarbonyl, alkylsulphinyl, alkylsulphonyl or dialkylamino,the alkyl part of these groups comprising 1 to 6 carbon atoms;

alkenyl or alkynyl containing 2 to 6 carbon atoms;

cycloalkyl containing 3 to 7 carbon atoms;

phenyl or benzyl, optionally substituted by a substituent chosen fromthe group comprising a halogen atom or a cyano, alkyl, alkoxy, haloalkylor haloalkoxy containing 1 to 9 halogen atoms, alkylcarbonyl oralkoxycarbonyl group, the alkyl part of these groups comprising 1 to 6carbon atoms;

R₃ is a group:

Het, Het-alkyl(containing 1 to 6 carbon atoms), or Het-alkenyl orHet-alkynyl(each containing 3 to 6 carbon atoms), optionally substitutedby a substituent chosen from the group comprising a halogen atom or acyano, alkyl, alkoxy, haloalkyl or haloalkoxy containing 1 to 9 halogenatoms, alkylcarbonyl or alkoxycarbonyl group, the alkyl part of thesegroups comprising 1 to 6 carbon atoms;

in which Het is a heterocyclic radical containing 5 to 7 atoms, of which1 to 3 are heteroatoms (nitrogen, oxygen or sulphur), optionallysubstituted by a substituted chosen from the group comprising a halogenatom or a cyano, alkyl, alkoxy, haloalkyl or haloalkoxy containing 1 to9 halogen atoms alkylcarbonyl or alkoxycarbonyl group, the alkyl part ofthese groups comprising 1 to 6 carbon atoms;

dialkylaminoalkyl, the alkyl part of these groups comprising 1 to 6carbon atoms; cycloalkyl or cycloalkylalkyl (alkyl containing 1 to 4carbon at&ms) containing 3 to 7 carbon atoms; or phenethyl, optionallysubstituted by a substituent chosen from the group comprising a halogenatom, a cyano group, or an alkyl or alkoxy group each containing 1 to 4carbon atoms;

R₂ and R₃ can additionally form, with the nitrogen atom to which theyare joined, a nitrogen-containing ring containing 6 atoms, 4 of whichare carbon atoms, optionally substituted, and the fifth is a carbon atomor a heteroatom such as oxygen, sulphur or nitrogen which can besubstituted by an alkyl group containing 1 to 6 carbon atoms, it beingpossible for the nitrogen-containing ring itself to be substituted byone or two substituents chosen from the group comprising cyano,alkylcarbonyl, alkoxycarbonyl, mono- or dialkylaminocarbonyl,alkylsulphinyl or alkylsulphonyl, the alkyl part of these groupscomprising 1 to 6 carbon atoms, or phenylsulphinyl or phenylsulphonyl;

d) a group (CH₂)_(m) --R₄, in which:

m is equal to 1 or 2,

R₄ is a cyano, nitro, alkylcarbonyl, phenylcarbonyl, alkoxycarbonyl,mono- or dialkylaminocarbonyl, P(O)(alkoxy)₂, P(O)(benzyloxy)₂,P(O)(phenoxy)₂, trialkylsilyl or phenyl group, it being understood thatthe alkyl radical of these groups comprises 1 to 4 carbon atoms and isoptionally halogenated and that the phenyl nucleus of the aromaticradicals can be substituted by 1 to 5 substituents chosen from the groupcomprising a halogen atom, a nitro group or an alkyl, alkoxy, haloalkyl,haloalkoxy or alkoxycarbonyl radical, the alkyl part of each of theseradicals comprising 1 to 4 carbon atoms;

e) a group CH(R₅)--X--R₆, in which:

R₅ is a hydrogen atom or an alkyl containing 1 to 4 carbon atoms,

X is an oxygen atom or a group S(O)_(n), in which:

n is an integer equal to zero or two,

R₆ is:

alkyl containing 1 to 4 carbon atoms, optionally substituted by asubstituent chosen from the group comprising a halogen atom or a cyano,alkoxy, phenoxy, benzyloxy or trialkylsilyl group, the alkyl part ofeach of these radicals comprising 1 to 4 carbon atoms and the phenylnuclei being able to be substituted by 1 to 5 substituents chosen fromthe group comprising a halogen atom, a nitro group or an alkyl, alkoxy,haloalkyl or haloalkoxy radical, the alkyl part of each of theseradicals comprising 1 to 4 carbon atoms;

alkenyl or alkynyl containing 3 to 6 carbon atoms;

phenyl or benzyl, which can be substituted by 1 to 5 substituents chosenfrom the group comprising a halogen atom, a nitro-group or an alkyl,alkoxy, haloalkyl or haloalkoxy radical (1 to 4 carbon atoms);

f) a group CHR₇ R₈, in which:

R₇ is a hydrogen atom or a haloalkyl or alkoxy group, each containing 1to 4 carbon atoms,

R₈ is a halogen atom or a hydroxyl, alkoxy or O--C(O)R₉ group with

R₉ being a hydrogen atom, an alkyl, haloalkyl or alkenyl containing 1 to4 carbon atoms, tetrahydrofuryl, tetrahydropyranyl or alkoxycarbonylgroup, the alkyl part of each of these radicals comprising 1 to 6 carbonatoms;

g) a group C(X)--R₁₀, in which:

X is an oxygen or sulphur atom,

R₁₀ is:

a hydrogen or halogen atom,

an alkyl group containing 1 to 6 carbon atoms, optionally substituted bya substituent chosen from the group comprising a halogen atom or acyano, nitro, alkylcarbonyl, alkoxycarbonyl or mono- ordialkylaminocarbonyl group, the alkyl part of each of these radicalscomprising 1 to 4 carbon atoms, or a cycloalkyl group containing 3 to 6carbon atoms;

an alkenyl or alkynyl group, containing 3 to 6 carbon atoms, optionallysubstituted by a phenyl which can be substituted by 1 to 5 substituentschosen from the group comprising a halogen atom, a nitro group or analkyl, alkoxy, haloalkyl or haloalkoxy radical, the alkyl part of eachof these radicals comprising 1 to 4 carbon atoms;

a phenyl, benzyl, 2-pyridyl, 3-pyridyl or 4-pyridyl group, it beingpossible for the nuclei to be substituted by 1 to 5 substituents chosenfrom the group comprising a halogen atom, a nitro or cyano group, or analkyl, alkoxy, haloalkyl, haloalkoxy, alkylcarbonyl or alkoxycarbonylradical, the alkyl part of each of these radicals comprising 1 to 4carbon atoms;

a group CH(R₁₁)--X--R₁₂, in which:

R₁₁ is a hydrogen atom or an alkyl containing 1 to 4 carbon atoms,

X is an oxygen atom or the group S(O)_(p), with p equal to zero or 2;

R₁₂ is an alkyl containing 1 to 4 carbon atoms, optionally substitutedby a halogen atom or an alkoxy containing 1 to 4 carbon atoms; analkenyl or alkynyl group, containing 3 to 6 carbon atoms; a phenyl orbenzyl group which can be substituted by 1 to 5 substituents chosen fromthe group comprising a halogen atom, a nitro group or an alkyl, alkoxy,haloalkyl or haloalkoxy radcial (1 to 4 carbon atoms);

a group CH(R₁₁)--NR₁₃ R₁₄, in which R₁₃ and R₁₄, which are identical ordifferent, are each:

an alkyl containing 1 to 4 carbon atoms, optionally substituted by acyano, alkylcarbonyl, alkoxycarbonyl or dialkylaminocarbonyl group,halogen atom or an alkoxy containing 1 to 4 carbon atoms;

a phenyl or benzyl group which can be substituted by 1 to 5 substituentschosen from the group comprising a halogen atom, a nitro or cyano groupor an alkyl, alkoxy, haloalkyl, haloalkoxy or alkoxycarbonyl radical,the alkyl part of each of these radicals comprising 1 to 4 carbon atoms;

a group CHR₁₁ --R₁₅, in which:

R₁₁ is as defined above and

R₁₅ is a heterocyclic group NC₄ R₁₆ R₁₇ T, in which R₁₆ and R₁₇, whichare identical or different, are a hydrogen atom or an alkyl oralkoxycarbonyl group, each containing 1 to 3 carbon atoms, and T is anoxygen or sulphur atom, or a carbonyl or N--R₁₈ group, in which R₁₈, isa hydrogen atom or an alkyl formyl, alkylcarbonyl or alkoxycarbonylgroup, the alkyl part of each of these radicals comprising 1 to 4 carbonatoms;

h) a group --C(O)--X--R₁₉, in which:

X is an oxygen or sulphur atom,

R₁₉ is:

an alkyl group containing 1 to 6 carbon atoms, optionally substituted bya substituent chosen from the group comprising a halogen atom or a cyanogroup; a cycloalkyl group containing 3 to 6 carbon atoms, optionallysubstituted by an alkyl containing 1 to 3 carbon atoms; trialkylsilyl,phenylsulphonyl, optionally substituted by at least one halogen atom oran alkyl group; alkoxycarbonyl or dialkylaminocarbonyl; the alkyl partof each of the above radicals comprising 1 to 4 carbon atoms;

an alkenyl or alkynyl group containing 2 to 6 carbon atoms, optionallysubstituted by a phenyl which can be substituted by 1 to 5 substituentschosen from the group comprising a halogen atom, a nitro group or analkyl radical;

a phenyl, benzyl, 2-pyridyl, 3-pyridyl or 4-pyridyl group, it beingpossible for the nuclei to be substituted by 1 to 5 substituents chosenfrom the group comprising a halogen atom, a nitro or cyano group, or analkyl, alkoxy, haloalkyl, haloalkoxy, alkylcarbonyl or alkoxycarbonyl,alkylthio, alkylsulphinyl or alkylsulphonyl radical, the alkyl part ofeach of these radicals comprising 1 to 4 carbon atoms;

a phenylalkyl group or a heterocyclylalkyl group, in which the alkylpart comprises 1 to 4 carbon atoms and the heterocyclyl part can be2-pyridyl, 3-pyridyl, 4-pyridyl, 2- furyl, 3-furyl, 2-thienyl or3-thienyl, it being possible for the nuclei to be substituted by 1 to 5substituents chosen from the group comprising a halogen atom a nitrogroup, or an alkyl alkoxy, haloalkyl, haloalkoxy, alkylcarbonyl oralkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl radical;

i) a group C(X)--NR₂₀ R₂₁, in which:

X is an oxygen or sulphur atom,

R₂₀ and R₂₁ are each:

a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms,optionally substituted by a substituent chosen from the group comprisinga halogen atom or a cyano, alkylcarbonyl, alkoxycarbonyl ordialkylaminocarbonyl group, the alkyl part of each of the above radicalscomprising 1 to 4 carbon atoms;

a cycloalkyl group containing 3 to 6 carbon atoms, optionallysubstituted by an alkyl containing 1 to 3 carbon atoms,

an alkenyl or alkynyl group containing 3 to 6 carbon atoms,

a phenyl or benzyl group, it being possible for the nuclei of each tosubstituted by 1 to 5 substituents chosen from the group comprising ahalogen atom, a nitro or cyano group, or an alkyl, alkoxy, haloalkyl,haloalkoxy, alkylcarbonyl or alkoxycarbonyl, alkylthio, alkylsulphinylor alkylsulphonyl radical, the alkyl part of each of these radicalscomprising 1 to 4 carbon atoms;

R₂₀ and R₂₁ can additionally form, with the nitrogen atom to which theyare joined, a ring containing 6 atoms, 4 of which are optionallysubstituted carbon atoms and the fifth of which is a carbon atom or aheteroatom such as oxygen, sulphur or nitrogen;

j) a group SiR₂₂ R₂₃ R₂₄, in which R₂₂, R₂₃ and R₂₄, which are identicalor different, are each an alkyl group containing 1 to 4 carbon atoms, ora phenyl or benzyl group,

k) a group P(X)R₂₅ R₂₆, in which:

X is an oxygen or sulphur atom,

R₂₅ and R₂₆, which are identical or different, are each an alkyl oralkoxy group containing 1 to 4 carbon atoms, or a phenyl, phenoxy,benzyl or benzoxy group.

In the formula, X is preferably a chlorine or bromine atom.

Other preferred derivatives are such that, in the formulae I and Ia, Yand/or Z are a hydrogen or chlorine atom.

Other preferred derivatives are such that, in the formulae I and Ia, Yand Z together form a bridge comprising 3 or 4 atoms.

Other preferred derivatives are such that, in the formulae I and Ia, Yand Z form an optionally halogenated methylenedioxy bridge.

Other preferred derivatives are such that, in the formulae I and Ia, Ris an alkyl(1 to 3 carbon atoms)carbonyl, alkoxy(1 to 3 carbonatoms)carbonyl, phenylcarbonyl or phenoxycarbonyl.

The derivatives according to the invention can be prepared by variousprocesses known per se, especially in the compilations "ComprehensiveHeterocyclic Chemistry", A. R. Katritzky and C. W. Rees, 1984, Vol. 5,pages 239 to 241 and 263, Pergamon Press; "Advances in HeterocyclicChemistry", A. N. Kost and I. I. Grandberg, 1966, Vol. 6, pages 391 to396, Academic Press and "The Chemistry of Heterocyclic Compounds", L. C.Behr, R. Fusco and C. H. Jardoe, 1967, J. Wiley & Sons.

A first process consists in reacting a 3-phenylpyrazole of formula II,in which Y and Z have the same meaning as in the formula I, with ahalogenating agent.

As halogenating agent, there may be mentioned, as chlorinating agent,chlorine, preferably in aqueous medium, such as in water, or in anorganic medium such as acetic acid or carbon tetrachloride, or elsehypochlorous acid, hydrochloric acid in the presence of hydrogenperoxide in acetic acid, or else sulphuryl chloride or an N-chloroimide,such as N-chlorosuccinimide, in a chlorinated solvent such asdichloromethane or else phosphorus pentachloride.

Chlorination can be carried out with chlorine in organic solvent medium,preferably a lower carboxylic acid, at a temperature from 16° to 30° C.,preferably at room temperature, the tea&rants being in a substantiallystoichiometric molar ratio. Chlorination can also be carried out withN-chlorosuccinimide in organic solvent medium, preferably a chlorinatedsolvent such as dichloromethane or 1,2-dichloroethane, at a temperatureof 0° C. to 80° C. and preferably from 20° C. to 50° C., the reactantsbeing in a substantially stoichiometric molar ratio.

There may be cited, as brominating agent, bromine, preferably in anaqueous solvent such as water, in acidic medium, for example nitric oracetic acid, in the presence or absence of a base such as sodiumacetate, or in an organic solvent, such as, for example, chloroform, orelse pyridinium perbromide.

Bromination can be carried out, for example, with bromine in organicsolvent medium such as a lower carboxylic acid, at a temperature of 16°C. and preferably at room temperature.

There can be used, as iodinating agent, iodine in the presence ofhypoiodous acid or in the presence of a base such as an alkali metalhydroxide or a basic salt such as sodium acetate, or in the presence ofa nickel(II) salt. It is also possible to use iodine with the silver(I)salt of the pyrazole of formula I. It is also possible to useN-iodosuccinimide, as indicated above for N-chlorosuccinimide.

Fluorination can be carried out from derivatives of formula V, in whichY and Z have the same meaning as in the formula I by preparation of thediazonium tetrafluoroborate derivative derived from the 4-amino groupand then by irradiation of this compound.

A second process known per se for the preparation of the derivatives offormula I according to the invention consists in reacting a4-formyl-3-phenylpyrazole of formula IV with bromine in acetic acid togive 4-bromo-3-phenylpyrazole.

The compounds of formula II can be prepared, in a very known per se, byreaction with hydrazine of a derivative of formula III, in which X is ahydrogen atom and W is a hydroxyl radical or a chlorine atom and Y and Zhave the same meanings as in the formula I.

It is also possible to prepare, in a way known per se, the derivativesof formula II from derivatives of formula III, in which X is a hydrogenatom and W a dialkylamino group, Y and Z being defined as above, byreaction with hydrazine hydrate at a temperature of 10° C. to 150° C.,preferably from 60° C. to 120° C., advantageously in organic solventmedium, preferably a lower carboxylic acid or in an alcohol in thepresence of an organic or inorganic acidic catalyst, the molar ratio ofthe 2 reactants being substantially stoichiometric.

The derivatives of formula III, in which X is a hydrogen atom and W adialkylamino group, Y and Z being defined as above, can be obtained, ina way known per se, by reaction of acetophenones of formula VI, in whichY and Z are defined as above, with amide acetals, ester aminals ororthoaminals, preferably in the absence of organic solvent with dialkyl(preferably dimethyl or diethyl) acetals of N,N-dimethylformamide, at atemperature of 20° C. to 130° C. and preferably from 70° C. to 130° C.

The following examples are given in order to illustrate the preparationand the fungicidal activity of the derivatives according to theinvention. The structure of the latter was Confirmed by NMR analysis.

EXAMPLE 1

25 g (0.162 mol) of 2'-chloroacetophenone are dissolved, at roomtemperature and with stirring, in 60 ml of N,N-dimethylformamidedimethyl acetal. Stirring is maintained and the reaction mixture isheated for 4 h 30 at 80° C. The mixture is concentrated to dryness underreduced pressure. The residue is taken up in 150 ml of methylenechloride. The resulting organic solution is washed with water, driedover MgSO₄ and then concentrated. The residue is chromatographed on asilica column (eluent: heptane/ethyl acetate 50/50). 27.0 g (0.129 mol)of 1-(2-chlorophenyl)-3-dimethylamino-2-propen-1-one (compound 1) (yield80%), the structure of which is confirmed by NMR, was obtained in ahoney-like consistency.

EXAMPLE 2

By carrying out the preparation as in Example 1 but by using theappropriate reactants, the derivatives of formula III collated in thefollowing Table A were obtained:

    ______________________________________                                                                             M.p. (°C.)                        COMPOUND                             or                                       No.       Y          Z         Yield analysis                                 ______________________________________                                         2        F          H         66    NMR                                       3        H          Cl        63    72                                        4        Cl         Cl        87    89                                        5*       OCF.sub.2  O         76    84                                        6        SCH.sub.3  H         95    NMR                                       7        CH.sub.3   H         69    NMR                                       8        H          CH.sub.3  73    45                                       27        nc.sub.3 H.sub.7                                                                         Cl        100   NMR                                      28        CH.sub.3   CF.sub.3  100   NMR                                      29        H          OCF.sub.3 95    NMR                                      30        OCH.sub.3  Cl        97    NMR                                      31        Cl         Br        91    114                                      32        H          CF.sub.3  79    62                                       33        C.sub.2 H.sub.5                                                                          Cl        80    94                                       34        F          Br        75    54                                       35        H          CN        93    118                                      36        O(CH.sub.2).sub.2                                                                        O         65    NMR                                      37        SOCH.sub.3 Cl        93    102                                      38        Cl         F         88    72                                       39        CH.sub.3   Cl        84    76                                       40        F          Cl        83    64                                       41        OCH.sub.2  O         57    118                                      42        F          CF.sub.3  72    59                                       43        OCH.sub.3  OCH.sub.3 83    NMR                                      44        F          F         79    62                                       45        CH.sub.3   H         69    NMR                                      46        H          F         84    73                                       47        naphthyl   naphthyl  100   oil                                      48        NO.sub.2   Cl        73    170                                      49        C.sub.6 H.sub.5 CH.sub.2 O                                                               H         68    75                                       50        CH.sub.3   CH.sub.3  65    solid                                    51        Cl         NO.sub.2  73    116                                      52        H          NO.sub.2  67    105                                      53        NO.sub.2   H         80    132                                      54        H          Br        89    oil                                      55        (CH.sub.3).sub.3 Si                                                                      Cl        83    honey                                    --        CH.sub.2                                                            56        Br         H         99    oil                                      57        CF.sub.3   H         98    oil                                      58        NO.sub.2   CH.sub.3  95    161                                      59        C.sub.2 H.sub.5 O                                                                        Cl        100   honey                                    ______________________________________                                         *Here and throughout these Examples, where Y is indicated as OCF.sub.2 an     Z as O, Y and Z are joined to form a --OCF.sub.2 O-- radical, and             analogously for Y═O(CH.sub.2).sub.2 and Z═O, and so forth.       

EXAMPLE 3

7 g (0.0540 mol) of hydrazine hydrate are added, slowly and at roomtemperature, to a solution of 10.5 g (0.050 mol) of1-(2-chlorophenyl)-3-dimethylamino-2-propen-1-one, prepared in Example1, in 60 ml of ethanol. The reaction mixture is stirred for 5 hours atroom temperature then left standing for 12 hours before beingconcentrated to dryness. The residue is recrystallised from aheptane/ethyl acetate mixture. 6.9 g (0.0386 mol) of3-(2'-chlorophenyl)-1H-pyrazole are obtained, which melts at 93° C.(yield 77%) (compound 60).

EXAMPLE 4

By carrying out the preparation as in Example 3 but by using theappropriate reactants, the derivatives of formula II, collated in thefollowing Table B, were obtained:

    ______________________________________                                                                             M.p. (°C.)                        COMPOUND                             or                                       No.       Y          Z         Yield analysis                                 ______________________________________                                        10        F          H         73     51                                      11        H          Cl        96     84                                      12        Cl         Cl        90    121                                      13        OCF.sub.2  O         80    130                                      14        SCH.sub.3  H         53     90                                      15        CH.sub.3   H         92    NMR                                      16        H          CH.sub.3  61    NMR                                      61        nC.sub.3 H.sub.7                                                                         Cl        41    NMR                                      62        H          OCF.sub.3 87     98                                      63        OCH.sub.3  Cl        94    100                                      64        Cl         Br        50    160                                      65        H          CF.sub.3  86     67                                      66        C.sub.2 H.sub.5                                                                          Cl        63     77                                      67        F          Br        75    121                                      68        H          CN        90     85                                      69        CF.sub.3   H         67    73                                       70        SOCH.sub.3 Cl        86    168                                      71        Cl         F         100   120                                      72        CH.sub.3   Cl        87     74                                      73        F          Cl        81    103                                      74        OCH.sub.2  O         91     50                                      75        F          CF.sub.3  90     86                                      76        OCH.sub.3  OCH.sub.3 86     90                                      77        F          F         86     90                                      78        CH.sub.3   H         93    NMR                                      79        H          F         76     77                                      80        naphthyl   naphthyl  81    119                                      81        NO.sub.2   Cl        46    173                                      82        C.sub.6 H.sub.5 CH.sub.2 O                                                               H         83     62                                      83        CH.sub.3   CH.sub.3  66     79                                      84        Cl         NO.sub.2  93    117                                      85        H          NO.sub.2  70    126                                      86        NO.sub.2   H         95     80                                      87        H          Br        89    106                                      88        (CH.sub.3).sub.3 Si                                                                      Cl        56    honey                                              CH.sub.2                                                            89        Br         H         72    134                                      90        CF.sub.3   H         67     72                                      91        NO.sub.2   CH.sub.3  81    137                                      92        NO.sub.2   SC.sub.6 H.sub.5                                                                        8     164                                      93        C.sub.2 H.sub.5 O                                                                        Cl               96                                      ______________________________________                                    

EXAMPLE 5

3.5 g of 3-(2-chlorophenyl)-1H-pyrazole, prepared as in Example 9, aredissolved, at room temperature and with stirring, in 20 ml of aceticacid. A solution of 3.76 g (0.0235 mol) of bromine in 20 ml of aceticacid is then run dropwise into the reaction mixture. Stirring ismaintained for 1 hour at room temperature and then the acetic acid andthe excess bromine are driven off under reduced pressure. The residue istaken up in methylene chloride and this organic solution is washed withan aqueous bicarbonate solution, then with water and then dried overMgSO₄ before being concentrated to dryness. The residue isrecrystallised from pentane. 3.3 g (0.0128 mol) of3-(2'-chlorophenyl)-4-bromo-1H-pyrazole are obtained, which melts at 80°C. (yield 65%) (compound 94)

EXAMPLE 6

By carrying out the preparation as in Example 5 but by using theappropriate reactants, the derivatives of formula I, in which X is abromine atom, collated in the following Table C, were obtained:

    ______________________________________                                        COMPOUND                    Yield                                                                              M.p. (°C.) or                         No.         Y        Z      %    analysis                                     ______________________________________                                        18          F        H      54   NMR                                          19          H        Cl     95   119                                          20          Cl       Cl     86   140                                          21          OCF.sub.2                                                                              O      50   144                                          95          NO.sub.2 Cl     44   190                                          ______________________________________                                    

EXAMPLE 7

6.8 g (0.038 mol) of 3-(2'-chlorophenyl)-1H-pyrazole, prepared as inExample 9, are dissolved, at temperature and with stirring, in 30 ml ofacetic acid. 2.9 g (0.0409 mol) of chlorine are then introduced into thereaction mixture. Stirring is maintained for 1 hour at room temperatureand then the acetic acid is driven off under reduced pressure. Theresidue is taken up in methylene chloride and this organic solution iswashed with in aqueous bicarbonate solution, then with water and thendried over Na₂ SO₄ before being concentrated to dryness. The residue ischromatographed on a silica column (eluent: heptane/ethyl acetate60/40). 3.6 g of 3-(2'-chlorophenyl)-4-chloro-1H-pyrazole (compound 96)are obtained, which is of honey-like consistency (yield 44%).

EXAMPLE 8

2.3 g (0.015 mol) of 3-(3-methylphenyl)-1H-pyrazole are dissolved in 45ml of dichloromethane at room temperature and with stirring. 2.1 g(0.016 mol) of N-chlorosuccinimide are then added and stirring is thencontinued for 60 hours at room temperature. The reaction mixture is thenconcentrated and then chromatographed on a silica column (eluent:heptane/ethyl acetate 80/20). 1.4 g (0.007 mol) of4-chloro-3-(3-methylphenyl)-1H-pyrazole (compound 97) is obtained whichmelts at 109° C. (yield 50%).

EXAMPLE 9

By carrying out the preparation as in Example 8, using the appropriatereactants, the derivatives of formula I in which X is a chlorine atom,collated in the following Table D, were obtained:

    ______________________________________                                        COMPOUND                      Yield M.p. (°C.) or                      No.      Y          Z         %     analysis                                  ______________________________________                                        24       Cl         Cl        53    140                                       25       OCF.sub.2  O         40    147                                       26       CH.sub.3   H         88    NMR                                       98       nC.sub.3 H.sub.7                                                                         Cl        47    NMR                                       99       CH.sub.3   CF.sub.3  68    NMR                                       100      H          OCF.sub.3 54     62                                       101      OCH.sub.3  Cl        44     70                                       102      Cl         Br        65    142                                       103      H          CF.sub.3  100    81                                       104      C.sub.2 H.sub.5                                                                          Cl        83     84                                       105      F          Br        88    114                                       106      H          CN        79    110                                       107      O(CH.sub.2).sub.2                                                                        O         74    NMR                                       108      CF.sub.3   H         40    111                                       109      SOCH.sub.3 Cl        41    171                                       110      Cl         F         94    105                                       111      CH.sub.3   Cl        28    NMR                                       112      F          Cl        46    120                                       113      OCH.sub.2  O         85    100                                       114      F          CF.sub.3  67     97                                       115      OCH.sub.3  OCH.sub.3 20     90                                       116      F          F         68     95                                       117      CH.sub.3   H         88    NMR                                       118      H          F         57    120                                       119      naphthyl   naphthyl  77    170                                       120      NO.sub.2   Cl        80    186                                       121      C.sub.6 H.sub.5 CH.sub.2 O                                                               H         89     91                                       122      CH.sub.3   CH.sub.3  33     89                                       123      H          Cl        13    122                                       124      Cl         NO.sub.2  70    162                                       125      H          NO.sub.2  85    148                                       127      NO.sub.2   H         91    honey                                     128      H          Br        80    151                                       129      (CH.sub.3).sub.3 Si                                                                      Cl        87     92                                                CH.sub.2                                                             130      NO.sub.2   CH.sub.3 S                                                                              60    honey                                     131      NO.sub.2   N(CH.sub.3).sub.2                                                                       40    honey                                     132      NH.sub.2   Cl        71    121                                       133      Br         H         92    honey                                     134      NO.sub.2   CH.sub.3  46    169                                       135      C.sub.2 H.sub.5 O                                                                        Cl               96                                       136      NO.sub.2   SC.sub.6 H.sub.5                                                                        8     164                                       ______________________________________                                    

EXAMPLE 10 4-Iodo-3-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrazole(compound 137)

1.03 g (0.0046 mol) of N-iodosuccinimide are added to a solution of 1 g(0.0045 mol) of the corresponding 4H-pyrazole obtained in Example 13 in50 ml of dichloroethane. The reaction mixture is stirred for 12 hours atroom temperature and then concentrated to dryness. The residue obtainedis purified by passing through a silica column with a heptane/ethylacetate 7/3 mixture as eluent to obtain a white powder, of melting point142° C., with a yield of 79.5%.

EXAMPLE 11 3-(2-Chlorophenyl)-4-cyanopyrazole

10 g (0.0055 mol) of 2-chlorobenzoylacetonitrile are dissolved at roomtemperature and with stirring in 30 ml of N,N-dimethylformamide dimethylacetal according to the procedure described in Example No. 1. 7.5 g(0.032 mol) of the compound thus obtained(3-(2-chlorophenyl)-2-cyano-1-dimethylamino-1-propen-3-one, yield 96%)are dissolved in 80 ml of acetic acid and then 2 ml (0.04 mol) ofhydrazine hydrate are added according to the procedure described inExample No. 1. After trituration in heptane, 4.1 g of3-(2-chlorophenyl)-4-cyanopyrazole (compound 138) are obtained:

Yield 63%, M.p.=160° C.

EXAMPLE 12 4-Ethoxycarbonyl-3-(2-chlorophenyl)pyrazole (compound 139)

2.04 g (0.01 mol) of 3-(2-chlorophenyl)-4-cyanopyrazole, obtainedaccording to Example No. 3, are treated with 2.4 ml of 95% ethanol and1.1 ml of concentrated H₂ SO₄ and are maintained at reflux for 6 hours.The reaction mixture is poured into water and then extracted with CH₂Cl₂. The organic phase is dried over MgSO₄, and then concentrated. Theresidue obtained is purified by passing through a silica column (CH₂ Cl₂/MeOH 98/2) to obtain a pale yellow oil:

Yield 36%. NMR analysis No. 42280.

EXAMPLE 13 3-(2-Chlorophenyl)-4-thiocarbamoylpyrazole (compound 140)

1 g (0.005 mol) of 3-(2-chlorophenyl)-4-cyanopyrazole, obtainedaccording to Example 11, and 0.75 g (0.01 mol) of thioacetamide aresuccessively added to a solution of 10 ml of DMF which is saturated withgaseous hydrochloric acid. The reaction mixture is maintained at 100° C.for 2 hours, then cooled to room temperature and poured into water. Thereaction mixture is then washed with an aqueous sodium bicarbonatesolution and then extracted with CH₂ Cl₂. After drying the organic phaseover MgSO₄ and evaporating, the residue obtained is purified by passingthrough a silica column (heptane/ethyl acetate 1/1) in order to obtain apale yellow powder:

Yield 36% M.p.=215° C.

EXAMPLE 14 4-Cyano-3-(2,2-difluoro-1,3-benzodioxol-4yl)-pyrazole(compound 141)

The intermediate 3-oxo-3-(2,2-difluoro-1,3-benzodioxol-4-yl)propanonitrile is obtained according to the method described inSynthesis, 1983, 308 by J. C. Krauss, T. L. Cupps, D. S. Wise and L. B.Townsend by condensation of the anion of cyanoacetic acid with thechloride of (2,2-difluoro-1,3-benzodioxol-4-yl)carboxylic acid obtainedaccording to the procedure described in the patent EP 333658. 5 g (0.022mol) of 3-oxo-3-(2,2-difluoro-1,3-benzodioxol-4-yl)-propanonitrile arethen dissolved in 10 ml of N,N-dimethylformamide dimethyl acetal and thesolution is heated at 70° C. The 5.7 g (0.022 mol) of the compound thusobtained(2-cyano-3-(2,2-difluoro-1,3-benzodioxol-4yl)-1-dimethylamino-1-propen-3-one)are dissolved in 50 ml of acetic acid and then treated with 1.5 ml(0.025 mol) of hydrazine hydrate. After passing through a silica column(heptane/ethyl acetate 6/4), 2.42 g of a pale yellow powder areobtained:

Yield 44% M.p.=175° C.

EXAMPLE 15 3-(2,2-Difluoro-1,3-benzodioxol-4-yl)-4-formylpyrazole(compound 142)

1.1 g (0.0044 mol) of 4-cyano-3-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrazole obtained above in Example No. 14 are dissolved in 10 ml oftoluene under a nitrogen atmosphere at -65° C. and 5.74 ml (0.0057 mol)of diisobutylaluminium hydride in solution in toluene are added. Afterstirring for 30 minutes at -70° C., the reaction mixture is broughtprogressively to room temperature and then stirred for 3 hours. Thereaction mixture is then hydrolysed with a saturated aqueous ammoniumchloride solution and then with a 10% aqueous hydrochloric acid solutionto a pH of 4. After extracting with ethyl acetate, the organic phase isdried over MgSO₄ and evaporated. The oil thus obtained is triturated ina heptane/diisopropyl ether mixture in order to obtain a yellow powder.

Yield 50%. M.p.=115° C.

EXAMPLE 16 3-(2,2-Difluoro-1,3-benzodioxol-4-yl)-4-methylpyrazole(compound 143)

12 g of 1-(2,2-difluoro-1,3-benzodioxol-4-yl)propanone are prepared bycondensation-of N,N-dimethylpropionamide with the lithiated anion of2,2-difluoro-1,3-benzodioxole obtained according to the proceduredescribed in patent EP 333658, are then dissolved in 14.6 ml (0.11 mol)of N,N-dimethylformamide dimethyl acetal and heated at 70° C. accordingto the procedure described in Example No. 1. 25 g (0.05 mol) ofenaminone thus obtained are dissolved in 130 ml of acetic acid and then3.3 ml (0.069 mol) of hydrazine hydrate are added. The crude productobtained is purified by trituration in pentane.

Yield 27%. M.p.=93° C.

EXAMPLE 17 3-(2,2-Difluoro-1,3-benzodioxol-4-yl)-4-nitropyrazole(compound 144)

6 ml of concentrated sulphuric acid and then, in portions, 1.92 g (0.019mol) of KNO₃ are successively added at 0° C. to a solution of 3 g (0.013mol) of pyrazole (Y═H), obtained according to Example No. 1 describedabove, in 60 ml of dichloroethane. The reaction mixture is then stirredat 0° C. for 1 hour, then brought to room temperature and stirred for 40minutes. The reaction mixture is precipitated by addition of ice andthen filtered in order to obtain a beige powder.

Yield 50%. M.p.=135° C.

EXAMPLE 18 3-(2,2-Difluoro-1,3-benzodioxol-4-yl)-4-pyrazolediazoniumtetrafluoroborate compound (145)

3-(2,2-Difluoro-1,3-benzodioxol-4-yl)-4-nitropyrazole obtained above inExample 17 is reduced to4-amino-3-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrazole according to themethod described by Vogel (Practical Organic Chemistry, Fourth Editionp. 660: Fe/HCl). 0.8 g (0.003 mol) of4-amino-3-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrazole in solution in 10ml of anhydrous THF is treated at 0° C. with a solution of 10 ml of THFcontaining 1 ml (0.0081 mol) of boron trifluoride etherate 0.6 ml (0.005mol) of tert-butyl nitrite in solution in 5 ml THF are then added to thereaction mixture. Stirring is maintained for 1 hour at 0° C., thereaction mixture is then diluted with pentane and filtered on a sinteredglass. After drying, a beige powder is obtained.

Yield 37%. M.p.=210° C.

EXAMPLE 19 4-Acetyl-3-(2,2-difluoro-1,3-benzodioxol4-yl)pyrazole(compound 146)

8 g (0.04 mol) of 4-acetyl-(2,2-difluoro-1,3-benzodioxole) obtainedaccording to patent EP 333658 in solution in 20 ml of ether are added toa suspension of 3.2 g (0.08 mol) of 60% sodium hydride in 30 ml of ethercontaining 7 g (0.08 mol) of ethyl acetate. The end of the addition isfollowed by heating the reaction mixture at reflux for 2 hours. Thereaction mixture is diluted with 50 ml of ether and then 2 ml ofabsolute ethanol and 20 ml of water are added in order to destroy theexcess NaH. The pH of the reaction mixture is then brought to 6 byaddition of a 1N aqueous hydrochloric acid solution. After extractingwith ether, drying over MgSO₄, evaporation and purification by passingthrough a silica column (heptane/ethyl acetate 9/1), 5 g of a paleyellow powder, 1-(2,2-difluoro-1,3-benzodioxol-4-yl)-1,3-butanedione,are obtained.

Yield 52%. M.p.=85° C.).

2.04 g (0.0084 mol) of the latter compound are then dissolved in 1.23 ml(0.0092 mol) of N,N-dimethylformamide dimethyl acetal according to theprocedure described in Example No. 1 and heated at 70° C. according tothe procedure described in Example No. 1 and then treated, afterisolation of the intermediate enaminone, with 0.43 ml (0.0092 mol) ofhydrazine hydrate according to the procedure described in Example No. 1.The desired compound is separated from the reaction mixture by silicacolumn chromatography (heptane/ethyl acetate 6/4):

Yield 23%. M.p.=108° C.

EXAMPLE 20 4-Methylthio-3-(2-nitro-3-chlorophenyl)pyrazole (compound147)

7 g (0.035 mol) of 2'-nitro-3'-chloroacetophenone, in solution in 50 mlof acetic acid, are treated with 1.81 ml (0.0354 mol) of bromine at roomtemperature. After stirring for 12 hours, evaporation of the acetic acidleads to a yellow precipitate being obtained:2'-nitro-3'-chloro-2-bromoacetophenone:

Yield 85%.

1.5 g (0.0061 mol) of 2'-nitro-3'-chloro-2-(methylthio)acetophenone areprepared by addition at 0° C. of 1.3 g (0.018 mol) of sodiummethanethiolate in solution in 10 ml of methanol to 4.7 g (0.0168 mol)of 2'-nitro-3'-chloro-2-bromoacetophenone obtained above.

1.5. g (0.0061 mol) of 2'-nitro-3'-chloro-2-(methylthio)acetophenone aredissolved in 1.6 ml (0.012 mol) of N,N-dimethylformamide dimethyl acetalaccording to the procedure described in Example No. 1 and are heated at70° C. and then, after isolation of the intermediate enaminone, aretreated with 2 ml (0.042 mol) of hydrazine hydrate according to theprocedure described in Example No. 1. After purification by passingthrough a silica column (heptane/ethyl acetate 75/25), 600 mg of thedesired compound are obtained:

Yield 36%. M.p=169° C.

EXAMPLE 21 3-(3-Bromophenyl)-4-(methylsulfonyl)pyrazole (compound 147)

27.8 g (0.1 mol) of 3'-bromoacetophenone in solution in 300 ml ofacetonitrile are treated with 10.2 g (0.1 mol) of sodiummethylsulphinate and maintained at reflux for 8 hours. After cooling andevaporating the acetonitrile, the reaction mixture is washed with waterand extracted with CH₂ Cl₂. The crude residue obtained is purified bytrituration in diisopropyl ether and leads to a yellow powder beingobtained: (3'-bromo)(methylsulphonyl)acetophenone:

Yield 87%. M.p.=104° C.

1.1 g (0.004 mol) of (3'-bromo)(methylsulphonyl)acetophenone isdissolved in 20 ml (0.14 mol) of N,N-dimethylformamide dimethyl acetaland heated to 70° C. and then, after isolation of the intermediateenaminone, treated with 0.3 ml (0.006 mol) of hydrazine hydrateaccording to the procedure described in Example 1. After purification bytrituration in diisopropyl ether, a beige powder is obtained:

Yield 44%. M.p.=140° C.

EXAMPLE 22 3-(2,2-Difluoro-1,3-benzodioxol-4-yl)-4-thiocyanatopyrazole(compound 148)

2.3 ml (0.048 mol) of hydrazine hydrate are added to a toluene solution(80 ml) containing 9.03 g (0.04 mol) of3-oxo-3-(2,2-dichloro-1,3-benzodioxol-4-yl)propanonitrile, preparedaccording to Example No. 6, and 3.8 g (0.02 mol) ofpara-toluenesulphonic acid. The reaction mixture is heated at 80° C. for2 hours. After cooling to room temperature, the reaction mixture isdiluted with ethyl acetate, washed with water and with a saturatedsodium chloride solution. After drying over MgSO₄, evaporation of theorganic phase leads to a white powder being obtained which is purifiedby trituration in ether:5-amino-3-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrazole.

Yield 62%. M.p.=152° C.

0.45 ml (0.0088 mol) of bromine in methanolic solution (5 ml), cooledbeforehand to -70° C., is added to a solution of 1.63 g (0.0168 mol) ofpotassium thiocyanate in 15 ml of methanol, cooled to -70° C. 1.92 g(0.008 mol) of 5-amino-3-(2,2-difluoro-1,3-benzodioxol-4yl)pyrazole insolution in 5 ml of methanol, cooled to -70° C., is then added whilemaintaining the temperature of the reaction mixture at -70° C. Stirringis maintained for 1 h 30 at -70° C. and then for approximately 30minutes at room temperature. Treatment of the reaction mixture iscarried out by addition of ethyl acetate, washing with water and with asaturated sodium chloride solution. After drying over MgSO₄, evaporationof the organic phase leads to the following being obtained:5-amino-3-(2,2-difluoro-1,3-benzodioxol-4-yl)-4-thilocyanatopyrazole.

Yield 80%. M.p.=264° C.

0.94 ml (0.008 mol) of tert-butyl nitrite in solution in 5 ml of THF isadded to a solution of 1.95 g (0.0065 mol) of5-amino-4-thiocyanato-3-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrazole in25 ml of THF at 0° C. The reaction mixture is stirred for 1 h 30 at roomtemperature, then diluted with ethyl acetate and washed with water.After drying over MgSO₄ and evaporating the solvent, the residueobtained is chromatographed on a silica column and leads to3-(2,2-difluoro-1,3-benzodioxol-4-yl)-1-(N-tetrahydrofuryl)-4-thiocyanatopyrazolebeing obtained.

Yield 20% (oil). Analysis No. 44694.

0.33 g (0.00094 mol) of the aminal obtained above is deprotected bybeing dissolved at room temperature in 10 ml of methanol treated with0.033 g (0.00018 mol) of para-toluenesulphonic acid. After stirring for1 hour at room temperature, the reaction mixture is diluted with ethylacetate and washed with a saturated sodium bicarbonate solution. Dryingover MgSO₄ and evaporation of the organic phase leads to a pale yellowpowder being obtained:3-(2,2-difluoro-1,3-benzodioxol-4-yl)-4-thiocyanatopyrazole:

Yield 98%. M.p.=163° C.

EXAMPLE 23 1-Methyl-3-(2,3-dichlorophenyl)-4-chloropyrazole (compound149)

1.5 g of 4-chloro-3-(2,3-dichlorophenyl) pyrazole and 0.40 g of dimethylmethylphosphonate are heated at 150° C. for 1 hour. After returning toroom temperature, the mixture is taken up in a saturated aqueous NaHCO₃solution and extracted with 2×50 ml of CH₂ Cl₂. The combined organicphases are dried over Na₂ SO₄ and concentrated under reduced pressure.The crude solid is purified by liquid chromatography on a silica column(eluent: heptane/ethyl acetate [80/20]).

EXAMPLE 24

The following 4-chloro-3(5)-(substituted)phenyl-1-R-pyrazoles offormulae I or Ia are prepared as in Example 23:

    ______________________________________                                        COMPOUND                           Ia    M.p. (°C.) or                 No.      Y       Z      R    I (%) (%)   analysis                             ______________________________________                                        150      OCF.sub.2                                                                             O      CH.sub.3                                                                           100         60                                   151      OCF.sub.2                                                                             O      CH.sub.3   100   oil                                  152      Cl      Cl     CH.sub.3   100   110                                  153      Cl      Cl     CH.sub.3                                                                           100         oil                                  154      Cl      H      CH.sub.3   100   66                                   ______________________________________                                    

EXAMPLE 251-Benzyl-3-(5)-(2,2-difluoro-1,3-dioxolano)phenyl-4-chloropyrazole(compound 155)

1.00 g of 4-chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole and 0.75g of benzyl bromide in 20 ml of absolute methanol are added to asolution of sodium methoxide prepared from 0.10 g of pieces of sodiumand 10 ml of absolute methanol at room temperature. The reaction mixtureis stirred for 12 hours at room temperature, concentrated to drynessunder reduced pressure and taken up in 80 ml of a water/ethyl acetate(1/1) mixture. The organic phase is dried over MgSO₄ and concentratedunder reduced pressure. The crude solid is purified by liquidchromatography on a silica column (eluent: heptane/ethyl acetate[80/20]).

    ______________________________________                                        COMPOUND                            Ia   M.p. (°C.) or                 No.      Y      Z     R        I (%)                                                                              (%)  analysis                             ______________________________________                                        156      OCF.sub.2                                                                            O     CH.sub.2 C.sub.6 H.sub.5                                                               70   30   oil                                  157      OCF.sub.2                                                                            O     SO.sub.2 N(CH.sub.3).sub.2                                                             100       50                                   ______________________________________                                    

EXAMPLE 261-(2-Cyanoethyl)-4-chloro-3-(2,2-difluoro-3-dioxolano)phenylpyrazole(compound 158)

1.00 g of 4-chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole and 0.20g of acrylonitrile are dissolved in 2.0 ml of dioxane. 0.02 ml of a 40%solution of Triton B in methanol is added. The reaction mixture isstirred for 12 hours at room temperature and concentrated to drynessunder reduced pressure. The residual solid is triturated with 10 ml ofheptane, recovered by filtration and dried under reduced pressure.

M.p.: 83° C.

EXAMPLE 271-[(Trimethylsilyl)methyl]-4-chloro-3-(2-nitro-3-chlorophenyl)pyrazole(compound 159)

0.85 g of anhydrous potassium carbonate is added to a solution of 1.30 gof 4-chloro-3-(2-nitro-3-chlorophenyl)pyrazole and 0.70 g of(trimethylsilyl)methyl chloride in 30 ml of N,N-dimethylformamide. Thereaction mixture is stirred for 12 hours at room temperature and dilutedwith 100 ml of an ether/H₂ O (1/1) mixture. The ether phase is driedover MgSO₄ and concentrated under reduced pressure. The residual oil ispurified by liquid chromatography on a Silica column (eluent:heptane/ethyl acetate [50/50]).

EXAMPLE 28

The following compounds are prepared as in Example 27:

    ______________________________________                                                                                  M.p. (°C.)                   COMPOUND                             Ia   or                                  No.      Y       Z     R       I (%) (%)  analysis                            ______________________________________                                        160      NO.sub.2                                                                              Cl    CH.sub.2 S--                                                                          80    20   88                                                         (pClC.sub.6 H.sub.4)                                   161      NO.sub.2                                                                              Cl    CH.sub.2 SCH.sub.3                                                                    80    20   65                                  162      NO.sub.2                                                                              Cl    CH.sub.2 OCH.sub.3                                                                    100        124                                 163      NO.sub.2                                                                              Cl    CH.sub.2 OCH.sub.3                                                                          100  128                                 164      NO.sub.2                                                                              Cl    CH.sub.2 O                                                                            100        57                                                         (CH.sub.2).sub.2 OCH.sub.3                             165      NO.sub.2                                                                              Cl    CH.sub.2 O                                                                            53    47   oil                                                        (CH.sub.2).sub.2 Si                                                           (CH.sub.3).sub.3                                       166      NO.sub.2                                                                              Cl    CH.sub.2 SCN                                                                          84    16   99                                  167      NO.sub.2                                                                              Cl    CH.sub.2 SO.sub.2                                                                     50    50   62                                                         CH.sub.3                                               168      NO.sub.2                                                                              Cl    CH.sub.2 (o-NO.sub.2                                                                        100  115                                                        C.sub.6 H.sub.4)                                       169      NO.sub.2                                                                              Cl    CH.sub.2 CO(4-                                                                        100        146                                                        CH.sub.3 OC.sub.6 H.sub.4)                             170      NO.sub.2                                                                              Cl    CH.sub.2 OCH.sub.2                                                                    80    20   84                                                         C.sub.6 H.sub.5                                        171      H       Cl    CH.sub.2 CH.sub.2 Cl                                                                  80    20   oil                                 ______________________________________                                    

EXAMPLE 291-(Chlorothioformyl)-4-chloro-(2,2-difluoro-1,3-dioxolano)phenylpyrazole(compound 172)

1.00 g of 4-chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole and 0.15ml of thiophosgene in solution in 50 ml of toluene are heated, at refluxof the thiophosgene (70° C.), for 2 hours. The reaction mixture isconcentrated to dryness under reduced pressure. The residue is purifiedby liquid chromatography on a silica column (heptane/AcOEt. [90/10]).

M.p.: 85° C.,

EXAMPLE 30 1-Benzoyl-4-chloro-3-(2,2-difluoro-3-dioxolano)phenylpyrazole(compound 173)

0.55 g of benzoyl chloride diluted in 10 ml of anhydrous THF are addeddropwise to a solution, cooled to +10° C., of 1.0 g of4-chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole, 0.08 g of DMAPand 0.55 ml of triethylamine in 20 ml of anhydrous THF. Stirring iscontinued for 2 hours at room temperature. The reaction mixture isconcentrated to dryness under reduced pressure and taken up in 80 ml ofan H₂ O-ethyl acetate (1/1) mixture. The organic phase is dried overMgSO₄ and concentrated under reduced pressure.

M.p.: 85° C.

EXAMPLE 31

The following compounds are prepared as in Example 30:

    ______________________________________                                        COMPOUND                         M.p. (°C.) or                         No.         Y      Z        R    analysis                                     ______________________________________                                        174         OCF.sub.2                                                                            O        COCH.sub.3                                                                          125                                         175         CH.sub.3                                                                             Cl       COCH.sub.3                                                                          63                                          176         NO.sub.2                                                                             Cl       COCH.sub.3                                                                          158                                         ______________________________________                                    

EXAMPLE 321-(Methoxycarbonyl)-4-chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole(compound 177)

5 ml of methyl chloroformate, diluted in 10 of anhydrous THF, are addeddropwise to a solution, cooled to 0° C., of 1.0 g of4-chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole, 0.08 g of DMAPand 0.55 mg of triethylamine in 20 ml of anhydrous THF. Sitrring iscontinued for 2 h at room temperature. The reaction mixture isconcentrated to dryness under reduced pressure and taken up in 80 ml ofa H₂ O--AcOEt (1/1) mixture. The organic phase is dried over MgSO₄ andconcentrated under reduced pressure.

Melting point: 75° C.

By carrying out the preparation as above,1-benzyloxycarbonyl-4chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole(compound 178) is obtained.

Melting point: 83° C.

EXAMPLE 331-(tert-Butyloxycarbonyl)-4-chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole(compound 179)

1.00 g of anhydrous di(tert-butyloxy)carbonyl, diluted in 10 g ofacetonitrile, is added dropwise to a solution of 1.0 g of4-chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole, 0.045 g of DMAP0.55 ml of triethylamine in 20 ml acetonitrile. Stirring is continuedfor 2 hours at room temperature. The reaction mixture is concentrated todryness under reduced pressure. The residual solid is purified by lividchromatography on a silica column (eluent: heptane/ethyl acetate[80/20]). The solid has the consistency of a foam.

EXAMPLE 341-(Phenoxycarbonyl-4-chloro-3-(2-nitro-3-chlorophenyl)pyrazole of(compound 180)

1.0 ml of phenyl chloroformate is added, in small portions, to asolution, cooled to 0° C., of 1.3 g of4-chloro-3-(2-nitro-3-chlorophenyl)pyrazole in 20 ml of pyridine.Stirring is continued for 8 hours at room temperature. The reactionmixture is concentrated dryness under reduced pressure and taken up in100 ml of an H₂ O/ethyl acetate (1/1) mixture. The organic phase isdried over MgSO₄ and concentrated under reduced pressure. The residualsolid is purified by recrystallisation from diisopropyl ether.

Melting point: 123° C.

EXAMPLE 35

The following compounds are prepared as in Example 34:

    ______________________________________                                        Compound                           M.p. (°C.) or                       No.         Y      Z       R       analysis                                   ______________________________________                                        181         NO.sub.2                                                                             Cl      C(O)S C.sub.2 H.sub.5                                                                 109                                        182         NO.sub.2                                                                             Cl      CO.sub.2 C(CH.sub.3).sub.2                                                            219                                                                   CO.sub.2 C.sub.2 H.sub.5                           183         NO.sub.2                                                                             Cl      CO.sub.2 CHCH.sub.2                                                                   118                                        184         NO.sub.2                                                                             Cl      CO.sub.2 (p-NO.sub.2                                                                  185                                                                   C.sub.6 H.sub.4)                                   185         NO.sub.2                                                                             Cl      CO.sub.2 CH.sub.2 CH                                                                  130                                                                   Cl.sub.2                                           ______________________________________                                    

EXAMPLE 361-Isopropylaminocarbonyl-4-chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole(compound 186)

0.45 g of isopropyl isocyanate is added dropwise to a solution of 1.0 gof 4-chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole and 0.50 g oftriethylamine in 20 ml of anhydrous DMF. Stirring is continued for 2hours at room temperature. The treatment is identical to that of Example32.

Melting point: 135° C.

EXAMPLE 371-(4-Methylphenylsulphonyl)-4-chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole(compound 187)

0.75 g of tosyl chloride is added, in small portions, to a solution of1.0 g of 4-chloro-3-(2,2-difluoro-1,3-dioxolano)phenylpyrazole and 0.5ml of pyridine in 20 ml of toluene. Stirring is continued for 2 hours at40° C. The treatment is identical to that of Example 32. The residualsolid is purified by liquid chromatography on a silica column (eluent:heptane/ethyl acetate [80/20]).

Melting point: 100° C.

EXAMPLE 38 In Vivo Test on Botrytis Cinerea on Excised Tomato Leaf(Strains Sensitive and Resistant to Benzimidazoles)

An aqueous suspension of the active material to be tested is prepared,by fine milling, having the following composition:

active materials: 60 mg

surface-active agent Tween 80 (oleate of polyoxyethylenated derivativeof sorbitan) diluted to 10% in water: 0.3 ml

made up to 60 ml with water.

This aqueous suspension is then diluted with water to obtain the desiredconcentration of active material.

Tomatoes cultivated under glass (variety Marmande), 30 days old, aretreated by spraying with aqueous suspensions as defined above and atvarious concentrations of the test compound.

After 24 hours, the leaves cut and put in a Petri dish (diameter 14 cm),the bottom of which was covered beforehand with a wet filter paper disc(10 leaflets per dish).

The inoculum is then introduced, using a syringe, by deposition of drops(3 per leaflet) of a suspension of spores of Botrytis cinerea, which aresensitive to benzimidazoles or resistant to benzimidazoles, obtainedfrom 15-day cultures and then suspended at a concentration of 150,000units per cm³.

Inspection is carried out 6 days after infection by comparison with anuntreated control.

Under these conditions, at a dose of 1 g/l, a good (at least 75%) ortotal protection is observed with the following compounds:

Botrytis sensitive to benzimidazoles: 9, 13, 17, 19, 21, 22, 23, 24, 25,71, 73, 74, 88, 95, 99, 100, 104, 105, 107, 108, 113, 114, 116, 120,122, 123, 124, 128, 133, 135, 147, 166, 172, 173, 175, 176, 177, 179,180, 181, 182, 183, 184, 185.

EXAMPLE 39 In Vivo Test on Piricularia Oryzae Responsible forPiriculariosis in Rice

An aqueous suspension of the active material to be tested is prepared,having the following composition:

active material: 60 mg

surface-active agent TWeen 80 (oleate of polyoxyethylenated derivativeof sorbitan) diluted to 10% in water: 0.3 ml

made up to 60 ml with water.

This aqueous suspension is then diluted with water to obtain the desiredconcentration of active material.

Rice, seeded in small pots in a 50/50 mixture of enriched peat andpozzolana, is treated at the 10 cm high stage by spraying with the aboveaqueous suspension.

After 24 hours, an aqueous suspension of spores of Piricularia oryzae,obtained from a 15-day culture and then suspended at a concentration of100,000 units per cm³, is applied to the leaves.

The rice plants are incubated for 24 hours (25° C., 100% relativehumidity) and are then put in an observation cell, under the sameconditions, for 7 days.

Reading is carried out 6 days after infection.

Under these conditions, at a dose of 1 g/l, a good (at least 75%) ortotal protection is observed with the following compounds:

12, 17, 19, 21, 24, 25, 72, 78, 81, 84, 87, 95, 99, 100, 101, 103, 104,105, 107, 108, 110, 111, 112, 113, 114, 116, 117, 118, 120, 122, 123,124, 127, 128, 129, 130, 133, 134, 135, 141, 166, 172, 173, 174, 175,176, 177, 179, 180, 181, 182, 183, 184, 185.

EXAMPLE 40 In vivo Test on Plasmopara Viticola

An aqueous suspension of the active material to be tested is prepared,by fine milling, having the following composition:

active material: 60 mg

surface-active agent Tween 80 (oleate of polyoxyethylenated derivativeof sorbitan) diluted to 10% in water: 0.3 ml

made up to 60 ml with water.

This aqueous suspension is then diluted with water to obtain the desiredconcentration of active material.

Vine cuttings (Vitis vinifera, variety Chardonnay) are cultivated insmall pots. When these plants are 2 months old (8 to 10 leaf stage, 10to 15 cm in height), they are treated by spraying with the above aqueoussuspension.

Plants used as controls are treated with an aqueous solution which doesnot contain the active material.

After drying for 24 hours, each plant is infected by spraying with anaqueous suspension of spores-of Plasmopara viticola, obtained from a17-day culture and then suspended at a concentration of 100,000 unitsper cm³.

The infected plants are then incubated for two days at approximately 18°C., in an atmosphere saturated with moisture and then for 5 days atapproximately 20°-22° C. at 90-100% relative humidity.

Reading is carried out 7 days after infection, by comparison with thecontrol plants.

Under these conditions, at a dose of 1 g/l, a good (at least 75%) ortotal protection is observed with the following compounds: 13, 19, 20,21, 22, 24, 25, 64, 74, 77, 80, 81, 82, 102, 104, 106, 107, 109, 111,113, 125, 127, 131, 133, 134, 139, 142, 144, 186.

These results clearly show the good fungicidal properties of thederivatives according to the invention against fungal diseases of plantsdue to fungi belonging to the most diverse families, such as thePhycometes, Basidiomycetes, Ascomycetes, Adelomycetes or FungiImperfecti, in particular the Botrytis species, Piricularia oryzae,Alternaria and grape downy mildew.

In fact, the compounds according to the invention are rarely used alonefor the practical use. These compounds are most often part ofcompositions. These compositions, which can be used as herbicidalagents, contain a compound according to the invention, as describedearlier, as active material mixed with solid or liquid vehicles, whichare acceptable in agriculture, and surface-active agents which are alsoacceptable in agriculture. In particular, the inert and conventionalvehicles and the conventional surface-active agents can be used. Thesecompositions also form part of the invention.

These compositions can also contain any kind of other ingredients suchas, for example, protective colloids, adhesives, thickening agents,thixotropic agents, penetrating agents, stabilising agents, sequesteringagents and the like. More generally, the compounds used in the inventioncan be combined with all the solid or liquid additives corresponding tothe conventional formulating techniques.

Generally, the compositions according to the invention usually containfrom approximately 0.05 to 95% (by weight) of a compound according tothe invention, one or more solid or liquid vehicles and, optionally, oneor more surface-active agents.

In the present account, the term "vehicle" denotes a natural orsynthetic, organic or inorganic material with which the compound iscombined facilitate its application to the plant, to seeds or to theground. This vehicle is thus generally inert and it must be acceptablein agriculture, especially on the treated plant. The vehicle can besolid (clays, natural or synthetic silicates, silica, resins, waxes,solid fertilisers and the like) or liquid (water, alcohols, especiallybutanol, and the like).

The surface-active agent can be an emulsifying, dispersing or wettingagent of ionic or nonionic type or a mixture of such surface-activeagents. There may be mentioned, for example, salts of polyacrylic acids,salts of lignosulphonic acids, salts of phenolsulphonic ornaphthalenesulphonic acids, polycondensates of ethylene oxide with fattyalcohols or with fatty acids or with fatty amines, substituted phenols,especially alkylphenols or arylphenols), salts of esters ofsulphosuccinic acids, taurine derivatives (especially alkyltaurates),phosphoric esters of polyoxyethylenated phenols or alcohols, esters offatty acids and polyols, and the derivatives of the above compoundscontaining sulphate, sulphonate and phosphate functional groups. Thepresence of at least one surface-active agent is generally indispensablewhen the compound and/or the inert vehicle is not soluble in water andthe carrier agent for application is water.

The compositions for agricultural use according to the invention canthus contain the active materials according to the invention within verywide limits, ranging from 0.05% to 95% (by weight). Their surface-activeagent content is advantageously of between 5% and 40% by weight.

These compositions according to the invention are themselves in fairlydiverse, solid or liquid forms.

There may be mentioned, as forms of solid compositions, the powders fordusting (with a content of compound which can range up to 100%) and thegranules, especially those obtained by extrusion, by compacting, byimpregnation of a granulated support, or by granulation from a powder(the content of compound in these granules being between 0.5 and 80% forthe latter cases).

The compounds of formula (I) can also be used in the form of powders fordusting; it is also possible to use a composition comprising 50 g ofactive material and 950 g of talc; it is also possible to use acomposition comprising 20 g of active material, 10 g of finely dividedsilica and 970 g of talc; these constituents are mixed and milled andthe mixture is applied by dusting.

There may be mentioned, as forms of liquid compositions or thoseintended to constitute liquid compositions at the time of application,solutions, in particular water-soluble concentrates, emulsifiableconcentrates, emulsions, suspension concentrates, aerosols, wettablepowders (or powder to be sprayed), or pastes.

The emulsifiable or soluble concentrates most often comprise 10 to 80%of active material while emulsions or solutions ready for applicationcontain 0.001 to 20% of active material.

In addition to the solvent, the emulsifiable concentrates can contain,when this is necessary, 2 to 20% of suitable additives such asstabilising agents, surface-active agents, penetrating agents, corrosioninhibitors, dyes or the abovementioned adhesives.

From these concentrates, it is possible to obtain, by dilution withwater, emulsions of any desired concentration, which are particularlysuitable for application to crops.

The compositions of some emulsifiable concentrates are given here asexamples:

EC Example 1:

    ______________________________________                                        active material        400      g/l                                           alkali metal dodecylbenzenesulphonate                                                                24       g/l                                           oxyethylenated nonylphenol, containing                                                               16       g/l                                           10 molecules of ethylene oxide                                                cyclohexanone          200      g/l                                           aromatic solvent       qs 1     liter                                         ______________________________________                                    

Another emulsifiable concentrate formula uses:

EC Example 2:

    ______________________________________                                        active material       250 g                                                   epoxidised vegetable oil                                                                             25 g                                                   mixture of alkylaryl sulphonate and                                                                 100 g                                                   ether of polyglycol and fatty alcohols                                        dimethylformamide      50 g                                                   xylene                575 g                                                   ______________________________________                                    

The suspension concentrates, also applicable in spraying, are preparedso as to obtain a stable fluid product which does not settle out andthey generally contain from 10 to 75% of active material, from 0.5 to15% of surface-active agents, from 0.1 to 10% of thixotropic agents andfrom 0 to 10% of suitable additives, such as antifoaming agents,corrosion inhibitors, stabilising agents, penetrating agents andadhesives and, as vehicle, water or an organic liquid in which theactive material is insoluble or nearly insoluble: certain organic solidmaterials or inorganic salts can be dissolved in the vehicle to aid inpreventing sedimentation or as antigels for water.

A suspension concentrate composition is given here as an example:

SC Example 1:

    ______________________________________                                        compound              500       g                                             polyethoxylated tristyrylphenyl                                                                     50        g                                             phosphate                                                                     polyethoxylated alkylphenol                                                                         50        g                                             sodium polycarboxylate                                                                              20        g                                             ethylene glycol       50        g                                             organopolysiloxane oil (antifoaming                                                                 1         g                                             agent)                                                                        polysaccharide        1.5       g                                             water                 316.5     g                                             ______________________________________                                    

Wettable powders (or powder to be sprayed) are generally prepared sothat they contain 20 to 95% of active material, and they generallycontain, in addition to the solid vehicle, from 0 to 30% of a wettingagent from 3 to 20% of a dispersing agent and, when this is necessary,from 0.1 to 10% of one or more stabilising agents and/or otheradditives, such as penetrating agents, adhesives, or anticlumpingagents, dyes, and the like.

To obtain powders to be sprayed or wettable powders, the activematerials are intimately mixed, in suitable mixers, with the additionalsubstances and the mixture is milled with mills or other suitablegrinders. Powders to be sprayed are thereby obtained with advantageouswettability and suspensibility; they can be suspended in water at anydesired concentration and these suspensions can be used veryadvantageously in particular for application to plant leaves.

Pastes can be produced in place of wettable powders. The conditions andmodes of production and use of these pastes are similar to those ofwettable powders or powders to be sprayed.

Various wettable powder (or powder to be sprayed) compositions are givenhere as examples:

WP Example 1:

    ______________________________________                                        active material (compound No. 1)                                                                       50%                                                  ethoxylated fatty alcohol (wetting agent)                                                             2.5%                                                  ethoxylated phenylethylphenol (dispersing                                                              5%                                                   agent)                                                                        chalk (inert vehicle)  42.5%                                                  ______________________________________                                    

WP Example 2:

    ______________________________________                                        active material (compound No. 1)                                                                     10%                                                    C13 branched-type synthetic oxo alcohol,                                                             0.75%                                                  ethoxylated with 8 to 10 molecules of                                         ethylene oxide (wetting agent)                                                neutral calcium lignosulphonate                                                                      12%                                                    (dispersing agent)                                                            calcium carbonate (inert vehicle)                                                                    qs 100%                                                ______________________________________                                    

WP Example 3:

This wettable powder contains the same ingredients as in the aboveexample, in the proportions below:

    ______________________________________                                        active material     75%                                                       wetting agent       1.50%                                                     dispersing agent    8%                                                        calcium carbonate (inert vehicle)                                                                 qs 100%                                                   ______________________________________                                    

WP Example 4:

    ______________________________________                                        active material (compound No. 1)                                                                      90%                                                   ethoxylated fatty alcohol (wetting agent)                                                             4%                                                    ethoxylated phenylethylphenol (dispersing                                                             6%                                                    agent)                                                                        ______________________________________                                    

WP Example 5:

    ______________________________________                                        active material (compound No. 1)                                                                     50%                                                    mixture of anionic and nonionic surface-                                                             2.5%                                                   active agents (wetting agent)                                                 sodium lignosulphonate (dispersing agent)                                                            5%                                                     kaolin clay (inert vehicle)                                                                          42.5%                                                  ______________________________________                                    

Aqueous dispersions and emulsions, for example the compositions obtainedby diluting a wettable powder or an emulsifiable concentrate accordingto the invention with water, are within the general scope of the presentinvention. Emulsions can be of the water-in-oil or oil-in-water type andthey can have a thick consistency, like that of a "mayonnaise".

The compounds according to the invention can be formulated in the formof water-dispersable granules, also within the scope of the invention.

These dispersible granules, with a bulk density generally of betweenapproximately 0.3 and 0.6, have a particle size generally of betweenapproximately 150 and 2000 and preferably between 300 and 1500 microns.

The active material content of these granules is generally betweenapproximately 1% and 90%, and preferably between 25% and 90%.

The rest of the granule is essentially composed of a solid vehicle and,optionally, of surface-active adjuvants which conferwater-dispersibility properties on the granule. These granules can beessentially of two distinct types according to whether the vehicle heldis soluble or insoluble in water. When the vehicle is water-soluble, itcan be inorganic or, preferably, organic. Excellent results wereobtained with urea. In the case of an insoluble vehicle, the latter ispreferably inorganic, such as, for example, kaolin or bentonite. It isthen advantageously accompanied by surface-active agents (in aproportion of 2 to 20% by weight of the granule) of which more than halfconsists of, for example, at least one dispersing agent essentiallyanionic, such as an alkali metal or alkaline-earth metalpolynaphthalenesulphonate or an alkali metal or alkaline-earth metallignosulphonate; the remainder consisting of nonionic or anionic wettingagents such as an alkali metal or alkaline-earth metalalkylnaphthalenesulphonate.

Moreover, although this is not indispensible, it is possible to addother adjuvants such as antifoaming agents.

The granules according to the invention can be prepared by mixing thenecessary ingredients and then granulating according to severaltechniques known per se (granulator, fluid bed, sprayer, extrusion, andthe like). The preparation generally finishes with a grinding followedby a sieving to the particle size chosen within the limits mentionedabove.

They are preferably obtained by extrusion, by carrying out thepreparation as indicated in the examples below.

F Example 6: Dispersible Granules

90% by weight of active material (compound No. 1) and 10% of urea in theform of pearls are mixed in a mixer. The mixture is then milled in a pinmill. A powder is obtained which is moistened with approximately 8% byweight of water. The moist powder is extruded in a perforated-rollerextruder. A granular material is obtained which is dried, and thencrushed and sieved, so as to respectively keep only the granules with asize of between 150 and 2000 microns.

F Example 7: Dispersible Granules

The following constituents are mixed in a mixer:

    ______________________________________                                        active material (compound No. 1)                                                                      75%                                                   wetting agent (sodium alkylnaphthalene-                                                                2%                                                   sulphonate                                                                    dispersing agent (sodium polynaphthalene-                                                              8%                                                   sulphonate)                                                                   water-insoluble inert vehicle (kaolin)                                                                15%                                                   ______________________________________                                    

This mixture is granulated on a fluid bed in the presence of water andthen dried, crushed and sieved so as to obtain granules with a size ofbetween 0.15 and 0.80 mm.

These granules can be used alone or in solution or dispersion in waterso as to obtain the required dose. They can also be used to preparecombinations with other active materials, especially fungicides, thelatter being in the form of wettable powders or granules or aqueoussuspensions.

As regards the compositions which are suitable for storage andtransportation, they most advantageously contain from 0.5 to 95% (byweight) of active substance.

Another subject of the invention is the use of the compounds accordingto the invention for combating fungal diseases in plants by preventativeor curative treatment of the latter or of their growth site.

While the invention has been described in terms of various preferredembodiments, the skilled artisan will appreciate that variousmodifications, substitutions, omissions, and changes may be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims, including equivalents thereof. ##STR3##

What is claimed:
 1. A compound of the formulawherein: X is:a hydrogen orhalogen atom, a nitro, cyano or thiocyanato group, a C₁ -C₄ alkyl, C₂-C₄ alkenyl, C₂ -C₄ alkynyl, C₁ -C₄ alkoxy or C₁ -C₄ alkylthio group,each of said groups being optionally halogenated, phenyl or phenoxy,each of which is optionally substituted by C₁ -C₃ alkyl, C₁ -C₃haloalkyl or C₁ -C₃ alkoxy, an amino group, optionally bearing one ortwo substituents selected from the group consisting of C₁ -C₄ alkyl andphenyl, a (C₁ -C₄ alkyl)carbonyl, carbamoyl, carboxyl or benzoyl group,a C₁ -C₄ alkylsulphinyl or C₁ -C₄ alkylsulphonyl group; each of Y and Z,which are identical or different, is:a hydrogen atom, provided that Yand Z cannot both be hydrogen, a halogen atom, a hydroxyl, nitro,nitroso, cyano or thiocyanato group, an amino group, optionally bearingone or two substituents selected from the group consisting of C₁ -C₄alkyl and phenyl, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄hydroxyalkyl, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl, C₁ -C₄ alkylsulphinyl orC₁ -C₄ alkylsulphonyl group, each of said groups being optionallyhalogenated, phenyl, phenyloxy, phenylthio or benzyl, each of which isoptionally substituted on the nucleus by C₁ -C₃ alkyl, C₁ -C₃ haloalkylor C₁ -C₃ alkoxy, a formyl, acetyl, (C₁ -C₄ alkyl)thiocarbonyl, (C₁ -C₄alkoxy)thiocarbonyl, mono- or di(C₁ -C₄ alkyl)aminocarbonyl, mono- ordi(C₁ -C₄ alkyl)aminothiocarbonyl, carboxyl, carboxylate or carbamoylgroup, the alkyl portion of said groups being optionally substituted byat least one halogen atom, or benzoyl, optionally substituted on thenucleus by C₁ -C₃ alkyl, C₁ -C₃ haloalkyl or C₁ -C₃ alkoxy; R is:a) ahydrogen atom, a nitro, amino, hydroxyl, cyano, C₁ -C₆ alkyl or C₁ -C₆haloalkyl group; b) a group S(O)_(m) --R₁, wherein:m is an integer equalto zero or two, and R₁ is:either, when m is equal to zero:a C₁ -C₆haloalkyl group, a phenyl or 3-pyridyl group, each of which isoptionally substituted by at least one halogen atom or one nitro, C₁ -C₄alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy group; or,when m is equal to two:a C₁ -C₆ alkyl or C₁ -C₆ alkoxy group, each ofwhich is optionally substituted by one or more halogen atoms or C₁ -C₃alkoxy groups; a C₃ -C₆ cycloalkyl group; a C₃ -C₆ alkenyl, C₃ -C₆alkynyl or C₃ -C₆ alkenoxy group; a phenyl group, optionally substitutedby 1 to 5 substituents selected from the group consisting of halogen,nitro, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy and C₁ -C₄haloalkoxy; c) a group CH₂ --NR₂ R₃, wherein:R₂ is:C₁ -C₆ alkyl,optionally bearing a substituent selected from the group consisting ofcyano, C₁ -C₆ alkoxy, C₃ -C₇ cycloalkyl, (C₁ -C₆ alkyl)carbonyl, (C₁ -C₆alkoxy)carbonyl, mono(C₁ -C₆ alkyl)aminocarbonyl, di(C₁ -C₆alkyl)aminocarbonyl, C₁ -C₆ alkylsulphinyl, C₁ -C₆ alkylsulphonyl anddi(C₁ -C₆ alkyl)amino; C₂ -C₆ alkenyl or C₂ -C₆ alkynyl; C₃ -C₇cycloalkyl; phenyl or benzyl, each of which optionally bears asubstituent selected from the group consisting of halogen, cyano, C₁ -C₆alkyl, C₁ -C₆ alkoxy, C₁ -C₆ haloalkyl having 1 to 9 halogen atoms, C₁-C₆ haloalkoxy having 1 to 9 halogen atoms, (C₁ -C₆ alkyl)carbonyl and(C₁ -C₆ alkoxy)carbonyl; R₃ is:a group Het, Het-(C₁ -C₆ alkyl), Het-(C₃-C₆ alkenyl) or Het-(C₃ -C₆ alkynyl), each of which optionally bears asubstituent selected from the group consisting of halogen, cyano, C₁ -C₆alkyl, C₁ -C₆ alkoxy, C₁ -C₆ haloalkyl having 1 to 9 halogen atoms, C₁-C₆ haloalkoxy having 1 to 9 halogen atoms, (C₁ -C₆ alkyl)carbonyl and(C₁ -C₆ alkoxy)carbonyl, wherein Het is a heterocyclic radical having 5to 7 atoms, of which 1 to 3 are heteroatoms selected from the groupconsisting of nitrogen, oxygen and sulphur, optionally bearing asubstituent selected from the group consisting of halogen, cyano, C₁ -C₆alkyl, C₁ -C₆ alkoxy, C₁ -C₆ haloalkyl having 1 to 9 halogen atoms, C₁-C₆ haloalkoxy having 1 to 9 halogen atoms, (C₁ -C₆ alkyl)carbonyl and(C₁ -C₆ alkoxy)carbonyl; di(C₁ -C₆ alkyl)amino(C₁ -C₆ alkyl), C₃ -C₇cycloalkyl, (C₃ -C₇ cycloalkyl)(C₁ -C₄ alkyl) or phenethyl, optionallybearing a substituent selected from the group consisting of halogen,cyano, C₁ -C₄ alkyl and C₁ -C₄ alkoxy; R₂ and R₃ can additionally form,with the nitrogen atom to which they are joined, a nitrogen-containingring having 6 atoms, 4 of which are carbon atoms, optionallysubstituted, and the fifth of which is a carbon atom or a heteroatomselected from the group consisting of oxygen, sulphur and nitrogen whichcan be optionally substituted by C₁ -C₆ alkyl, the nitrogen-containingring itself optionally bearing one or two substituents selected from thegroup consisting of cyano, (C₁ -C₆ alkyl)carbonyl, (C₁ -C₆alkoxy)carbonyl, mono(C₁ -C₆ alkyl)aminocarbonyl, di(C₁ -C₆alkyl)aminocarbonyl, C₁ -C₆ alkylsulphinyl, C₁ -C₆ alkylsulphonyl,phenylsulphinyl and phenylsulphonyl; d) a group (CH₂)_(m) --R₄,wherein:m is equal to 1 or 2, R₄ is cyano, nitro, (C₁ -C₄alkyl)carbonyl, phenylcarbonyl, (C₁ -C₄ alkoxy)carbonyl, mono(C₁ -C₄alkyl)aminocarbonyl, di(C₁ -C₄ alkyl)aminocarbonyl, P(O) (C₁ -C₄alkoxy)₂, P(O) (benzyloxy)₂, P(O) (phenoxy)₂, tri(C₁ -C₄ alkyl)silyl orphenyl, wherein the alkyl portions of said groups are optionallyhalogenated and the phenyl nucleus of the aromatic radicals optionallybears 1 to 5 substituents selected from the group consisting of halogen,nitro, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxyand (C ₁ -C₄ alkoxy)carbonyl; e) a group CH(R₅)--X--R₆, wherein:R₅ ishydrogen or C₁ -C₄ alkyl, X is an oxygen atom or a group S(O)_(n),wherein:n is an integer equal to zero or two, R₆ is:C₁ -C₄ alkyl,optionally bearing a substituent selected from the group consisting ofhalogen, cyano, C₁ -C₄ alkoxy, phenoxy, benzyloxy and tri(C₁ -C₄alkyl)silyl, the phenyl nuclei being optionally substituted by 1 to 5substituents selected from the group consisting of halogen, nitro, C₁-C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkyl and C₁ -C₄ haloalkoxy; C₃ -C₆alkenyl or C₃ -C₆ alkynyl; phenyl or benzyl, each of which optionallybears 1 to 5 substituents selected from the group consisting of halogen,nitro, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkyl and C₁ -C₄haloalkoxy; f) a group CHR₇ R₈, wherein:R₇ is a hydrogen atom or a C₁-C₄ haloalkyl or C₁ -C₄ alkoxy group, R₈ is a halogen atom or ahydroxyl, C₁ -C₆ alkoxy or O--C(O)R₉ group wherein:R₉ is hydrogen, C₁-C₆ alkyl, C₁ -C₆ haloalkyl, C₂ -C₄ alkenyl, tetrahydrofuryl,tetrahydropyranyl or (C₁ -C₆ alkoxy)carbonyl; g) a group C(X)--R₁₀,wherein:X is an oxygen or sulphur atom, R₁₀ is:a hydrogen or halogenatom, a C₁ -C₆ alkyl group, optionally bearing a substituent selectedfrom the group consisting of halogen, cyano, nitro, (C₁ -C₄alkyl)carbonyl, (C₁ -C₄ alkoxy)carbonyl, mono(C₁ -C₄alkyl)aminocarbonyl, di(C₁ -C₄ alkyl)aminocarbonyl and C₃ -C₆cycloalkyl; a C₃ -C₆ alkenyl or C₃ -C₆ alkynyl group, optionallysubstituted by a phenyl which optionally bears 1 to 5 substituentsselected from the group consisting of halogen, nitro, C₁ -C₄ alkyl, C₁-C₄ alkoxy, C₁ -C₄ haloalkyl and C₁ -C₄ haloalkoxy; a phenyl, benzyl,2-pyridyl, 3-pyridyl or 4-pyridyl group, the nuclei of each of whichoptionally bears 1 to 5 substituents selected from the group consistingof halogen, nitro, cyano, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkyl,C₁ -C₄ haloalkoxy, (C₁ -C₄ alkyl)carbonyl and (C₁ -C₄ alkoxy)carbonyl; agroup CH(R₁₁)--X--R₁₂, wherein:R₁₁ is a hydrogen atom or C₁ -C₄ alkylgroup, X is an oxygen atom or the group S(O)_(p), wherein p is equal tozero or 2; R₁₂ is C₁ -C₄ alkyl group, optionally substituted by ahalogen atom or C₁ -C₄ alkoxy group; a C₃ -C₆ alkenyl or C₃ -C₆ alkynylgroup; a phenyl or benzyl group, optionally bearing 1 to 5 substituentsselected from the group consisting of halogen, nitro, C₁ -C₄ alkyl, C₁-C₄ alkoxy, C₁ -C₄ haloalkyl and C₁ -C₄ haloalkoxy; a groupCH(R₁₁)--NR₁₃ R₁₄, wherein:R₁₁ is defined as above and each of R₁₃ andR₁₄, which are identical or different, is:C₁ -C₄ alkyl, optionallysubstituted by a cyano, (C₁ -C₄ alkyl)carbonyl, (C₁ -C₄ alkoxy)carbonyl,di(C₁ -C₄ alkyl)aminocarbonyl, halogen or C₁ -C₄ alkoxy; a phenyl orbenzyl group, each of which can optionally bear 1 to 5 substituentsselected from the group consisting of halogen, nitro, cyano, C₁ -C₄alkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy and (C₁ -C₄alkoxy)carbonyl; a group CHR₁₁ --R₁₅, wherein:R₁₁ is defined as aboveand R₁₅ is a heterocyclic group NC₄ R₁₆ R₁₇ T, wherein each of R₁₆ andR₁₇, which are identical or different, is a hydrogen atom or a C₁ -C₃alkyl or (C₁ -C₃ alkoxy)carbonyl group, and T is an oxygen or sulphuratom, or a carbonyl or N-R₁₈ group, wherein R₁₈ is a hydrogen atom or C₁-C₄ alkyl, formyl, (C₁ -C₄ alkylcarbonyl or (C₁ -C₄ alkoxy)carbonylgroup; h) a group --C(O)--X--R₁₉, wherein:X is an oxygen or sulphuratom, R₁₉ is:a C₁ -C₆ alkyl group, optionally bearing a substituentselected from the group consisting of a halogen atom and a cyano group;a C₃ -C₆ cycloalkyl group, optionally substituted by C₁ -C₃ alkyl; atri(C₁ -C₄ alkyl)silyl or phenylsulphonyl, optionally substituted by atleast one halogen atom or C₁ -C₄ alkyl; a (C₁ -C₄ alkoxy)carbonyl ordi(C₁ -C₄ alkyl)aminocarbonyl; a C₂ -C₆ alkenyl or C₂ -C₆ alkynyl group,each of which can optionally be substituted by phenyl, which canoptionally bear 1 to 5 substituents selected from the group consistingof a halogen atom, a nitro group and a C₁ -C₄ alkyl radical; a phenyl,benzyl, 2-pyridyl, 3-pyridyl or 4-pyridyl group, the nuclei of each ofwhich can optionally bear 1 to 5 substituents selected from the groupconsisting of halogen, nitro, cyano, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkyl, C₁ -C₄ haloalkoxy, (C₁ -C₄ alkyl)carbonyl, (C₁ -C₄alkoxy)carbonyl, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulphinyl and C₁ -C₄alkylsulphonyl; a phenylalkyl group or a heterocyclylalkyl group,wherein the alkyl portion has 1 to 4 carbon atoms and the heterocyclylportion is 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-furyl, 3-furyl, 2-thienylor 3-thienyl, the heterocyclyl nuclei optionally bearing 1 to 5substituents selected from the group consisting of halogen, nitro, C₁-C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, (C₁ -C₄alkyl)carbonyl, (C₁ -C₄ alkoxy)carbonyl, C₁ -C₄ alkylthio, C₁ -C₄alkylsulphinyl and C₁ -C₄ alkylsulphonyl; i) a group C(X)--NR₂₀ R₂₁, inwhich:X is an oxygen or sulphur atom, each of R₂₀ and R₂₁ is:a hydrogenatom or a C₁ -C₄ alkyl group, optionally bearing a substituent selectedfrom the group consisting of halogen, cyano, (C₁ -C₄ alkyl)carbonyl, (C₁-C₄ alkoxy)carbonyl and di(C₁ -C₄ alkyl)aminocarbonyl; a C₃ -C₆cycloalkyl group, optionally substituted by C₁ -C₃ alkyl; a C₃ -C₆alkenyl or C₃ -C₆ alkynyl group; a phenyl or benzyl group, the nuclei ofeach of which optionally bear 1 to 5 substituents selected from thegroup consisting of halogen, nitro, cyano, C₁ -C₄ alkyl, C₁ -C₄ alkoxy,C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, (C₁ -C₄ alkyl)carbonyl, (C₁ -C₄alkoxy)carbonyl, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulphinyl and C₁ -C₄alkylsulphonyl radical; R₂₀ and R₂₁ can additionally form, with thenitrogen atom to which they are joined, a ring having 6 atoms, 4 ofwhich are optionally substituted carbon atoms and the fifth of which isa carbon atom or a heteroatom selected from the group consisting ofoxygen, sulphur and nitrogen; j) a group SiR₂₂ R₂₃ R₂₄, wherein each ofR₂₂, R₂₃ and R₂₄, which are identical or different, is C₁ -C₄ alkyl,phenyl or benzyl; k) a group P(X)R₂₅ R₂₆, wherein:X is an oxygen orsulphur atom, each of R₂₅ and R₂₆, which are identical or different, isC₁ -C₄ alkyl, C₁ -C₄ alkoxy, phenyl, phenoxy, benzyl or benzoxy; withthe proviso that when X is a hydrogen atom and R is a hydrogen atom,then Y is not a hydroxyl group or an alkoxy group; and with the furtherproviso that when X is a hydrogen atom, R is a methyl group and Y is ahydroxyl group, then Z is not a hydrogen atom or a methyl group.
 2. Thecompound according to claim 1, having formula I.
 3. The compoundaccording to claim 1, wherein X is a chlorine or bromine atom.
 4. Thecompound according to claim 1, wherein each of Y and Z is a hydrogenatom or a chlorine atom, provided that Y and Z cannot both be hydrogen.5. The compound according to claim 3, wherein each of Y and Z is ahydrogen atom or a chlorine atom, provided that Y and Z cannot both behydrogen.
 6. The compound according to claim 1, wherein R is a hydrogenatom.
 7. The compound according to claim 1, wherein R is a groupC(X)--R¹⁰ wherein X is oxygen or sulphur and R₁₀ is as defined inclaim
 1. 8. The compound according to claim 7, wherein R is (C₁ -C₃alkyl)carbonyl or phenylcarbonyl.
 9. The compound according to claim 1,wherein R is a group --C(O)--X--R₁₉ wherein X is oxygen or sulphur andR₁₉ is as defined in claim
 1. 10. The compound according to claim 9,wherein R is (C₁ -C₃ alkoxy)carbonyl or phenoxycarbonyl.
 11. Thecompound according to claim 1, having the formula ##STR4## wherein: Y isCl and Z is Cl;Y is Cl and Z is Br; Y is Cl and Z is F; Y is CH₃ and Zis Cl; Y is F and Z is Cl; Y is F and Z is F; Y is CH₃ and Z is H; Y isnaphthyl and Z is naphthyl; Y is NO₂ arid Z is Cl; Y is --OCH₂ C₆ H₅ andZ is H; Y is Cl and Z is NO₂ ; Y is H and Z is Br; or Y is --CH₂Si(CH₃)₃ and Z is Cl.
 12. The compound according to claim 1, having theformula ##STR5## wherein: Y is H, Z is Cl and X is Br;Y is Cl Z is Cland X is Br; Y is NO₂, Z is Cl and X is Br; Y is CH₃, Z is CF₃ and X isCl; Y is H, Z is OCF₃ and X is Cl; Y is OCH₃, Z is Cl and X is Cl; Y isCl, Z is Br and X is Cl; Y is H, Z is CF₃ and X is Cl; Y is C₂ H₅, Z isCl and X is Cl; Y is F, Z is Br and X is Cl; Y is H, Z is CN and X isCl; Y is CF₃, Z is H and X is Cl; Y is SOCH₃, Z is Cl and X is Cl; Y isCl, Z is F and X is Cl; Y is CH₃, Z is Cl and X is Cl; Y is F, Z is Cland X is Cl; Y is F, Z is CF₃ and X is Cl; Y is F, Z is F and X is Cl; Yis CH₃, Z is H and X is Cl; Y is H, Z is F and X is Cl; Y is NO₂, Z isCl and X is Cl; Y is CH₃, Z is CH₃ and X is Cl; Y is H, Z is Cl and X isCl; Y is Cl, Z is NO₂ and X is Cl; Y is H, Z is NO₂ and X is Cl; Y isNO₂, Z is H and X is Cl; Y is H, Z is Br and X is Cl; Y is CH₂ Si(CH₃)₃,Z is Cl and X is Cl; Y is NO₂, Z is SCH₃ and X is Cl; Y is NO₂, Z isN(CH₃)₂ and X is Cl; Y is Br, Z is H and X is Cl; Y is NO₂, Z is CH₃ andX is Cl; or Y is OC₂ H₅, Z is Cl and X is Cl.
 13. The compound accordingto claim 1, which is selected from the group consistingof:4-ethoxycarbonyl-3-(2-chlorophenyl)pyrazole,4-methylthio-3-(2-nitro-3-chlorophenyl)pyrazole,3-(3-bromophenyl)-4-(methylsulphonyl)pyrazole, 1-(thiocyanato)methyl-4-chloro-3-(2-nitro-3-chlorophenyl)pyrazole,1-acetyl-4-chloro-3-(2-methyl-3-chlorophenyl)-pyrazole, and1-acetyl-4-chloro-3-(2-nitro-3-chlorophenyl)pyrazole.
 14. The compoundaccording to claim 1, having the formula ##STR6## wherein R is --C(O)OC₆H₅, --C(O)SC₂ H₅, --CO₂ C(CH₃)₂ CO₂ C₂ H₅, --CO₂ CHCH₂, --CO₂ (p--NO₂--C₆ H₄) or --CO₂ CH₂ CHCl₂.
 15. A fungicidal composition comprising afungicidally effective amount of a compound according to claim 1 and anagriculturally acceptable vehicle therefor.
 16. The compositionaccording to claim 15, further comprising an agriculturally acceptablesurface-active agent.